Water-insoluble aryl-azo aryl dyestuffs containing a thienyl or furyl carboxamido group

ABSTRACT

IN WHICH A REPRESENTS THE RADICAL OF A DIAZO COMPONENT, R REPRESENTS AN ALKYL GROUP HAVING AT MOST 4 CARBON ATOMS, OR A HYDROGEN ATOM, R1 REPRESENTS A HYDROGEN ATOM OR AN ALKYL GROUP THAT MAY BE SUBSTITUTED , R3 REPRESENTS A FIVE-MEMBERED HETEROCYCLIC RADICAL WHICH MUST BE SUBSTITUTED WHEN IT REPRESENTS A FURAN RING, AND X REPRESENTS A HYDROGEN ATOM AR AN ALKYL, ALKOXY, ARYLOXY OR ARYLMERCAPTO GROUP ARE USEFUL FOR DYEING POLYESTER FIBERS ORANGE TO VIOLET SHADES OF EXCELLENT FASTNESS TO LIGHT AND SUBLIMATION.   1-(A-N=N-),2-(R1-CO-N(-R)-),4-(R1-N(-R2)-),X-BENZENE-   WATER INSOLUBLE AZO DYESTUFFS OF THE FORMULA

United States Patent 3,632,565 WATER-INSOLUBLE ARYL-AZO ARYL DYESTUFFSCONTAINING A THIENYL 0R YL CAR- BOXAMIDO GROUP Hans-Joerg Angliker andRichard Peter, Basel, Switzerland, assignors to Ciba Limited, Basel,Switzerland No Drawing. Filed Sept. 4, 1968, Ser. No. 757,478 Claimspriority, application Switzerland, Sept. 7, 1967, 12,524/67 Int. Cl.C09b 29/08; D06p N08 US. Cl. 260152 8 Claims ABSTRACT OF THE DISCLOSUREWater insoluble azo dyestuffs of the formula l R2 IIICORa R The presentinvention is based on the observation that valuable water-insoluble azodyestuffs of the formula in which A represents the residue of a diazocomponent, R represents an alkyl group having not more than 4 carbonatoms or a hydrogen atom, R represents a hydrogen atom or an alkyl groupthat may be substituted, R represents an alkyl group that may besubstituted, R represents a five-membered heterocyclic residue whichmust be substituted when it represents a furan ring, and X represents ahydrogen atom or an alkyl, alkoxy, aryloxy or arylmercapto group, may beobtained by coupling the diazo compound of an amine with a couplingcomponent of the formula in which X, R, R R and R have the meaningsgiven above.

ice

Dyestuffs that are of special interest are those corresponding to theformula in which X, A, R R and R have the meanings given above and Arepresents a substituted benzene residue or a monocyclic or bicyclicheterocyclic residue. Dyestuffs in which X represents a methyl ormethoxy group or a hydrogen atom and R represents either a substitutedfuran ring or a substituted or unsubstituted thiophene ring areespecially preferred.

The groups R and R may be alkyl groups containing 1 to 4, preferably 2to 4 carbon atoms, for example, methyl, ethyl, n-propyl or n-butylgroups, which may be substituted in the usual manner, with groups suchas C alkoxy, hydroxy, nitro, C carbalkoxy, formylamino, acetaylamino,acetoxy, diacetoxy, C alkylsulfonyl, C alkyloxycarbonyloxy,B-(p-chlorobenzenesulfonyl)- ethyl, fi-methyl-carbamyloxyethyl,fl-phenylcarbamyloxyethyl, 'y-acetamido-propyl,8-(para-nitrophenoxy)-ethyl, f3 (parahydroxyphenoxy) ethyl,fl-(fl-acetylethoxycarbonyl)-ethyl, ,8-[([3'-cyano)-ethoxycarb0nyl]ethyl, 5- [(fl'-hydroxy)ethoxycarbonyl] ethyl, B-[(B'-methoxy)ethoxycarbonyH-ethyl, B [(,B-acetoxy)ethoxycarbonyl1- ethyl,B-carboxyethyl, fl-acetylethyl, 'y-aminopropyl, fl-diethylaminoethyl,fl-cyanoacetoxyethyl, B-benzoyl-hydroxyethyl,fi-phenoxy-benZoyl-hydroxyethyl and only one of R or R being hydrogen atany one time, for example, one or more benzyl or ,B-phenylethyl groups,halogenated alkyl groups, for example, fi-chloroethyl,p,;8,fl-trifluoroethyl or {Ly-dichloropropyl groups, fl-cyanoethylgroups, alkoxyalkyl groups, for example, fl-ethoxyethyl or 6-methoxybutyl groups, hydroxyalkyl groups, for example, fi-hydroxyethyland ,8,'y-dihydroxypropyl groups, nitroalkyl groups, for example,fi-nitroethyl groups, carbalkoxy groups, for example,fl-carbo-(methoxy-, ethoxy or propoxy)-ethyl groups (in which theterminal alkyl group may carry cyano, carbalkoxy, acyloxy and aminogroups) and [3- or 'y-carbo-(methoxyor ethoxy)-propyl groups,acylaminoalkyl groups, for example, fl-(acetylor formyl)- aminoethylgroups, acyloxyalkyl groups, for example, ,8- acetoxyethyl andB,'y-diacetoxypropyl groups, ,B-(alkylor aryl)-sulphonylalkyl groups,for example, ,B-methanesulfonylethyl, fi-ethanesulphonylethyl or,B-(para-chlorobenzenesulphonyl)-ethyl groups, alkyl orarylcarbamoyloxyalkyl groups, for example, [i-methyl-carbamyloxyethyland ,B-phenylcarbamyloxyethyl groups, alkyloxycarbonyloxyalkyl groups,for example, ,B-(methoxy-, ethoxyor isopropyloxy)-carbonyloxyethyl,'y-acetamidopropyl, fl-(paranitrophenoxy)-ethyl,fi-(para-hydroxyphenoxy)ethyl, B- (B-acetylethoxycarbonyl)-ethyl, ,8-[(,B-cyano, hydroxy-, methoxyor acetoxy-)ethoxycarbonyl]-ethy1,cyanoalkoxyalkyl, ,B-carboxyethyl, ,B-acetylethyl, 'y-aminopropyl, 8-diethylaminoethyl, fl-cyanoacetoxyethyl and ,B-benzoylor B (paraalkoxyor phenoxy-benzoyl)-hydroxyethyl groups.

The groups R and R preferably contain not more than 18 carbon atoms. Theresidues R and R are preferably alkyl groups substituted by hydroxy,alkoxy, cyanoalkoxy, acyloxy or cyano groups.

The residue R is a heterocyclic ring such as thionyl, tetrahydrofuryl,tetrahydrothionyl and substituted furyl or thionyl, wherein thesubstitutent is selected from the group consisting of alkyl of up to 4carbon atoms, chloro, carboxy, carbomethoxy, paranitrophenyl andparachlorophenyl, and which must be substituted when it contains anoxygen atom as hetero atom. Suitable substituents are, for example, arylgroups, alkyl groups containing not more than 4 carbon atoms, chlorineatoms or carboxyl groups, or an alkylene chain bound on both sides tothe hetero ring.

The diazo components preferably correspond to the formula in which Yrepresents a hydrogen or a halogen atom or an alkyl, alkoxy, nitro,cyano, carbalkoxy or arylsulphonyl group and Z represents a hydrogen ora halogen atom or an alkyl, alkoxy, phenoxy, cyano or trifiuoromethylgroup. More particularly, Y may be hydrogen, chloro, bromo, lower alkyl,lower alkoxy, nitro, cyano, lower carbalkoxy or phenylsulphonyl, and Zmay be hydrogen, chloro, bromo, lower alkyl, lower alkoxy, phenoxy,cyano or trifiuoromethyl.

The following amines are given as examples of diazo components:1-amino-4-chlorobenzene, 1-amino-4-bromobenzene,1-amino-4-methylbenzene, 1-amino-4nitrobenzene, 1-amino-4-cyanobenzene,l-amino-2,S-dicyanobenzene, 1-amino-4-methylsulphonylbenzene,1-amino-4-carbomethoxybenzene, 1-amino-2,4-dichlorobenzene,1-amino-2,4-dibromobenzene, 1-amino-2-methyl-4-chlorobenzene,1-amino-2-trifluoromethyl-4-chlorobenzene,1-amino-2-cyano-4-chlorobenzene, 1-amino-2-carbomethoxy-4-chlorobenzene,l-amino-Z-carbomethoxy-4-nitrobenzene, l-amino-2-chloro-4-cyanobenzene,1-amino-2-chlor0-4-nitrobenzene, 1-amino-2-phenoxy-4-nitrobenzene,1-amino-2-chloro-4-carbethoxybenzene,1-amino-2-chloro-4-methylsulphonylbenzene,1-amino-2-methylsulphonyl-4-chlorobenzene,1-amino2-methylsulphony1-4-nitr0benzene, 1-amino-2,4-dinitrobenzene,1-amino-2,4-dicyanobenzene, l-amino-2-cyanomethylsulphonylbenzene,1-amino-2,6-dichloro-4-cyanobenzene,1-amino-2,6-dichloro-4-nitrobenzene,1-amino-2,4-dicyano-6-chlofobenzene,1-arnino-2,4-dicyano-6-chlorobenzene, 1-amino-2,5,6-trinitrobenzene,1-amino-2,4-dinitro-6-chlorobenzene, and especially1-amino-2-cyano-4-nitrobenzene, 4-aminoazobenzene, 4-amino-3-nitro-1,1'-azobenzene, 4-amino-3-nitro-4-chloro-1,1-azobenzene,4-amino-3-nitro-2'-chloro-1,1-azobenzene,4-amino-3-nitro-2'-methoxy-1,1'-azobenzene, and4-amino-3-nitro-4-methyl-1,1-azobenzene.

The following are given as examples of heterocyclic diazo components:

Z-aminothiazole, Z-amino-S-nitrothiazole, 2-amino-5-cyanothiazole,2amino-4-methyl-S-nitrothiazole, 2-amino-4-methylthiazole,

2-amino-4-phenylthiazole, 2-amino-(4-chloro)-phenylthiazole,

2-amino= 4'-nitro -phenylthiazole, 2-amino-fi-chlorobenzthiazole,2-amino-6-cyanobenzthiazole, 2-amino-6-nitrobenzthiazole,Z-amino-1,3,4-thiadiazole, 2-amino-1,3,5-thiadiazole,3-methylmercapto-5-amino1,2,4-thiadiazole, and3-methylsulphony1-5-amino-1,2,4-thiadiazole.

The coupling components preferably correspond to the formulaO-mcmcmooomn l NHCORs in which X represents a hydrogen atom or an alkylor alkoxy group, such as hydrogen, methoxy, ethoxy or methyl, Rrepresents a five-membered heterocyclic residue, for example, anaromatic residue, for example, a furan or thiophene residue or asaturated residue, for example, a tetrahydrofuran or tetrahydrothiopheneresidue and R represents an alkyl, lower alkyl phenyl or heterocyclicresidue.

The following coupling components are given as examples:

The residues represented by the symbol R in the coupling components mayalso be derived from sulpholanecarboxylic acids of the formula CH;,CH2

COOH

CH2 CH2 so, which may carry further substituents bound to the sulpholanering, or they may be derived from pyrrole-2- carboxylic acid.

The single coupling component may also be replaced by a mixture ofdiiferent coupling components. In many cases, the afiinity andbuilding-up properties of the dyestutf mixtures so obtained are betterthan those of the unitary dyestufis.

Diazotization of the above-mentioned diazo components may be carried outby methods known per se, for example, with the aid of a mineral acid,especially hydrochloric acid, and sodium nitrite, or, for example, witha solution of nitrosyl-sulphuric acid in concentrated sulphuric acid.

Coupling may also be carried out by a method known per se, for example,in a neutral to acid medium, if necessary, in the presence of sodiumacetate or a similar buffer which influences the rate of coupling, or acatalyst, for example, pyridine or a salt thereof.

After coupling, the dyestuffs formed can easily be separated from thecoupling mixture, for example, by filtration, because they aresubstantially insoluble in water.

The dyestufis of the present invention are eminently suitable for dyeingand printing materials, especially fibres and fabrics, made, forexample, from cellulose triacetate, polyacrylonitrile and polyamides,but especially from aromatic polyesters. They produce on these materialsstrong dyeings possessing excellent properties of fastness, especiallyexcellent fastness to light, sublimation and rubbing. The dyeings mayalso be subjected to permanent press processing, for example, theKoratron process. Dyeing produced with the new dyestuffs which have beenthus Lreated display excellent fastness to wet treatments and eat.

. For dyeing, the new dyestuffs are advantageously used in a state offine division, and dyeing is carried out in the presence of a dispersingagent, for example, soap, sulphite cellulose waste liquor or a syntheticdetergent, or a combination of different wetting and dispersing agents.Prior to dyeing, it is generally advantageous to convert the dyestuffinto a dyeing preparation which contains a dispersing agent and thedyestufi in a form such that a fine dispersion is obtained when thepreparation is diluted with water. Such dyestuff preparations may beobtained in a known manner, for example, by reprecipitating the dyestufffrom sulphuric acid and grinding the suspension so obtained withsulphite cellulose waste liquor. If necessary, they may also be obtainedby grinding the dyestuff 1n a highly efficient grinding device in thedry or wet state in the presence or absence of a dispersing agent.

To obtain stronger dyeings on polyethylene terephthalate fibres it isgenerally advantageous to add a swelling agent to the dyebath, or moreespecially to carry out the dyeing process under superatmosphericpressure at a temperature above 100 C., for example, at 120 C. Suitableswelling agents are aromatic carboxylic acids, for example, benzoic acidand salicyclic acid; phenols for example, orthoor para-hydroxydiphenyl;aromatic halogen compounds, for example, chlorobenzene,orthodichlorobenzene and trichlorobenzene; and phenylmethylcarbinol ordiphenyl. When carrying out the dyeing process under superatmosphericpressure it is generally advantageous to render the dyebath slightlyacidic, for example, by the addition of a weak'acid, for example, aceticacid.

By virtue of their fastness to alkali, the new dyestuffs are alsospecially suitable for application by the so-called thermofixationprocess in which the material to be dyed is impregnated at a temperaturenot exceeding 60 C. with an aqueous dispersion of the dyestuif whichadvantageously contains 1 to 50% of urea and a thickening agent,especially sodium alginate, and then squeezed in the usual manner. Theimpregnated material is advantageously squeezed so as to retain 50 to100% of its dry weight of dye-liquor.

To fix the dyestutf, the material so impregnated is heated to atemperature above 100 C., for example, to a temperature within the rangeof from 180 to 220 C., advantageously after drying, for example, in acurrent of warm air.

The aforementioned thermofixation process is especially suitable for thedyeing of union fabrics made from polyester fibres and cellulosicfibres, especially cotton. In this case, in addition to the dyestufis ofthe invention, the padding liquor contains dyestuffs suitable for dyeingcotton, especially vat dyestufls, or reactive dyestuifs, that is to say,dyestuffs capable of being fixed on the cellulosic fibre with formationof a chemical bond, for example, dyestufis which contain achlorotriazine or chlorodiazine residue. In the latter case, it isgenerally advantageous to add an agent capable of binding acid to thepadding liquor, for example, an alkali metal carbonate, an alkali metalphosphate, an alkali metal borate or an alkali metal perborate, ormixtures thereof. When using vat dyestufis, the padded fabric must betreated after the heat treatment with an aqueous alkaline solution ofone of the reducing agents commonly used in vat dyeing.

By virtue of the fact that the dyestuffs of the invention reserve wellon wool, they are eminently suitable for dyeing union fabrics made frompolyester fibre and wool.

The dyeings obtained are advantageously subjected to an after-treatment,for example, by heating with an aqueous solution of a non-ionicdetergent.

The dyestuffs may also be applied by printing processes. In this methodof application a printing paste is used which contains, for example, inaddition to the usual printing adjuvants, for example, thickening andwetting agents, the finely divided dyestufr', if necessary, in admixturewith one of the above-mentioned cotton dyestuffs, if necessary, togetherwith urea and/or an agent capable of binding acid.

The following examples illustrate the invention. Unless otherwisestated, the parts and percentages are by weight.

EXAMPLE 1 0.7 part of sodium nitrite is introduced into 15 parts ofsulphuric acid and the batch is stirred. 1.63 parts of2-cyano-4-nitroaniline are then added at a temperature of 20 to 25 C.,the whole is stirred for one hour, discharged on to parts of ice and theexcess of nitrite is destroyed with sulphamic acid.

A solution of 3.9 parts of N-bis-acetoxyethyl-3- thienoylaminoaniline in25 parts by volume of dimethylformamide is added dropwise to thesolution so obtained at a temperature not exceeding 10 C., the batch isstirred for three hours and then neutralized with 30% NaOH. The dyestuffis then isolated by filtration and dried. It dyes polyester a violetshade.

EXAMPLE 2 1.73 parts of 2-chloro-4-nitroaniline was mixed with 20 partsof water and 3 parts by volume of concentrated hydrochloric acid, thebatch is cooled to 0 C. and then diazotization is effected with 6 partsby volume of 2 N- sodium nitrite solution. The batch is stirred for onehour, filtered, and the excess of nitrite is destroyed with sulphamicacid.

A solution of 3.9 parts of N-bis-acetoxyethyl-3-thienoylaminoaniline in25 parts by volume of dimethylformamide is added dropwise to thesolution so obtained at a temperature of 0 to 10 C., the batch isstirred for 3 hours and is then neutralized with 30% sodium hydroxidesolution. The dyestuflf of the formula is isolated by filtration anddried. It dyes polyester fibres a bluish red shade possessing excellentfastness to light and sublimation.

The following table lists components for further dyestuffs. Thedyestuffs may be obtained by coupling the diazo compounds of theanilines listed in Column I with the coupling components listed inColumn II. The shades obtained on polyester fibres are indicated inColumn III.

I II III 23 No, CH B1115.

O2N- NH: N

S NED-CO-h] fiJ-COOCH; CHCH 4 ON CH Bluish-violet.

l 1 CH3 OzN NH2 N NH-C O-(fi (ill-C 0 CH3 CH-CH PREPARATION OF THECOUPLING COMPONENTS (I) N-bis-(acetoxyethyl-3-(2'-thienoylamino)-aniline(a) N-bis-acetoxyethyl-3-nitroaniline.-226 parts of N-bis-fl-hydroxyethyl-3-nitroaniline, obtainable according to the processdescribed in Swiss patent specification No. 171,721, together with 250parts of acetic anhydride, are heated for 3 hours at 130 C., the glacialacetic acid is removed in vacuo, and the residue is distilled in a highvacuum. The product of the formula is obtained.

Calculated (percent): 54.19; H, 5.85; N, 9.03. Found (percent): 54.25;H, 5.78; N, 9.05.

(b) N-bis-fl-acetoxyethyl3-aminoaniline.620 parts ofN-bis-fi-acetoxyethyl-3-nitroaniline are hydrogenated in 2,000 parts ofabsolute alcohol in the presence of Pd/ carbon, the solvent is removedin vacuo, and the residue is distilled in a high vacuum. The product ofthe formula (H) N-bis- (acetoxyethyl) -3- (5-carbomethoxy-2'- thienoylamino) -aniline 21 parts of thiophene-iZ-carboxylic acid chloride-5-carboxylic acid methylester are used instead of 15.5 parts ofthiophene-Z-carboxylic acid chloride.

(III) N-bis- (acetoxyethyl -3- 5 '-para-nitrophenyl-2-furoylamino)-aniline The product of the formula 1 o r zn-c-o CC N02 H Hll 0 CHMCH is obtained by replacing the 15.5 parts of thiophene-Z-.carboxylic acid chloride in Example II With 27 parts of 5-(para-nitrophenyl)-furan-2-carboxylic acid chloride.

(IV) N-bis-(acetoxyethyl)-3-(2'-furoylamino)-aniline 14- parts offuran-Z-carboxylic acid chloride are used instead of 15.5 parts ofthiophene-Z-carboxylic acid chloride.

(V) N-bis-(acetoxyethyl)-3-(2'-tetrahydrofuroylamino)- aniline -14.5parts of tetrahydrofuran-Z-carboxylic acid chloride are used instead of15.5 parts of thiophene-Z-carboxylic acid chloride.

The other coupling components may be obtained in an analogous manner.

Dyeing procedure: 1 part of the dyestulr' obtained in the mannerdescribed in Example 1 is ground Wet With 2 parts of a 50% aqueoussolution of the sodium salt of 1,1 dinaphthylmethane 2,2 disulphonicacid and the batch is dried.

The dyestufi preparation so obtained is mixed with 40 parts of a 10%aqueous solution of the sodium salt of Nbenzyl-y-heptadecylbenzimidazole disulphonic acid, and then 4 parts of a40% acetic acid solution are added. A dyebath of 4,000 parts is preparedtherefrom by dilution with Water.

parts of cleaned polyester fibre material are entered into this dyebathat 50 C., the temperature is raised to to C. within half an hour anddyeing is carried out for one hour at that temperature in a closedvessel. The material is then rinsed Well. A strong, violet dyeingpossessing excellent fastness to light and sublimation is obtained.

We claim: 1. A water-insoluble azo dyestuff of the formula A-N=N -NIII-(3011a R in which A represents a diazo component of the benzeneseries, R represents hydrogen or alkyl having up to 4 carbon atoms, Rand R each represents hydrogen, un-

substituted or substituted alkyl containing up to 4 carbon atoms whereinthe substituent is selected from the group consisting of chloro, cyano,C alkoxy, hydroxy, nitro, C carbalkoxy, formylamino, acetylamino,acetoxy, diacetoxy C alkylsulfonyl, C alkyloxycarbonyloxy, fl-(p-chlorobenzensulfonyl)ethyl, p methyl carbamyloxyethyl,fi-phenylcarbamyloxyethyl, 'y-acetamido-propyl, fi- (para-nitrophenoxy)-ethyl, B (para hydroxyphenoxy)- ethyl,fi-(B-acetylethoxycarbonyl)ethyl, ,B-[Qi cyan0)- ethoxycarbonyl] ethyl,,8- fl-hydroxy ethoxycarbonyl] ethyl, [H fi-methoxy)ethoxycarbonyl]ethyl, B-[ (H-acetoxy)ethoxycarbonyl] ethyl, [3 carboxyethyl, pacetylethyl, 'y aminopropyl, ,6 diethylaminoethyl, 13 cyanoacetoxyethyl,fl-benzoyl-hydroxyethyl, fl-phenoxy-benzoylhydroxyethyl and only one ofR or R being hydrogen at any one time; R represents thienyl,tetrahydrofuryl, tetrahydrothienyl and substituted furyl or thienyl,wherein the substituent is selected from the group consisting of alkylof up to 4 carbon atoms, chloro, carboxy, carbomethoxy, paranitrophenyland parachlorophenyl, and X is hydrogen, methoxy, ethoxy or methyl.

2. A water-insoluble monoazo dyestufi as claimed in claim 1, wherein Rrepresents S-carbomethoxythienyl.

3. A water-insoluble monoazo dyestufi as claimed in claim 1,corresponding to the formula in which Y represents hydrogen, chloro,bromo, lower alkyl, lower alkoxy, nitro, cyano, lower carbalkoxy orphenylsulphonyl, Z represents hydrogen, chloro, bromo, lower alkyl,lower alkoxy, phenoxy, cyano or trifluoromethyl, R represents loweralkyl or phenyl.

4. A water-insoluble monoazo dyestuff as claimed in claim 1 of theformula 5. A water-insoluble monoazo dyestuff as claimed in claim 1 ofthe formula 14 6. A water-insoluble monoazo dyestufi? as claimed inclaim 1 of the formula 7. A water-insoluble monoazo dyestuff as claimedin claim 1 of the formula 8. A water-insoluble monoazo dyestuif asclaimed in claim 1 of the formula 0 CH OH References Cited UNITED STATESPATENTS 2,144,219 1/1939 Etzelmiller 260-152 2,543,745 3/1951 Grimmel eta1 260-152 X 2,852,305 9/1958 Long et a1. 260-152 3,157,667 11/1964 Kernet a1 260152 X 3,437,418 4/1969 Huey et al 260152 X 3,433,952 5/1969Anderau 260'l52 X FLOYD D. HIGEL, Primary Examiner US. Cl. X.R.

84, 27, 41 A, 41 B, 41 C, 50, 71; 117-138.8 R, 138.8 F, 138.8 UA, 143;26037 R, 37 N, 40 R, 41 R, 158 205, 207, 306.8 R 332.2 C, 347.3, 490

2 3 3 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION 3,632,565bated January u, 1 72 Inventor(s) HANS-JOERG ANGLIKER ET AL It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Patent: No.

Column l I, lines l5-2 L, amend the middle of the formula to read:

NH---C -C O CH-- Signed and sealed this 1st day of August 1972.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GUTTSCHALK Commissioner of PatentsAttesting Officer

